Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/26—Organic compounds containing nitrogen
  • C11D3/30—Amines; Substituted amines ; Quaternized amines
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/66—Non-ionic compounds
  • C11D1/835—Mixtures of non-ionic with cationic compounds
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/43—Solvents
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/004—Surface-active compounds containing F
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/66—Non-ionic compounds
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/66—Non-ionic compounds
  • C11D1/72—Ethers of polyoxyalkylene glycols

Definitions

• the present invention relates to compositions for cleaning hard surfaces, wherein said composition comprises both cleans the surface and prevents or retards further soiling of the surface.
• soil release agents including polymers, siloxanes and quaternary cationic surfactants in cleaning compositions so as to provide a secondary cleaning benefit. It is believed that these soil release agents function by deposition of a layer of polymer, siloxane or surfactant on the surface during cleaning. This layer of material is believed to facilitate further cleaning operations by reducing the extent to which soil adheres to the surface. Obviously, some care is needed in the choice of soil-release agents as cleaning compositions typically comprise surfactants whose primary purpose is to remove materials from the surface and it is important both that the cleaning function of the composition is not impaired by the presence of the soil-release agent and that the soil release agent can deposit in the presence of surfactant.
• surfactants whose primary purpose is to remove materials from the surface and it is important both that the cleaning function of the composition is not impaired by the presence of the soil-release agent and that the soil release agent can deposit in the presence of surfactant.
• compositions which further reduce the extent to which soil adheres to surfaces and provide further formulation flexibility, especially as regards the possibility of flocculation of the compositions in the presence of electrolytes and/or other minor components.
• the present invention provides an aqueous, hard-surface cleaning composition
• a surfactant mixture comprising:
• the cationic flourosurfactants present in the compositions of the present invention modify the surface energy of surfaces to which the composition is applied so as to raise the contact angle of soil subsequently deposited on the modified surface.
• Typical cleaning compositions falling within the present invention comprise, in addition to nonionic surfactant, a level of cationic fluorosurfactant which is effective to lower the surface energy of a surface cleaned with the composition to below 25 mN/m.
• compositions of the present invention comprise a cationic fluorosurfactant.
• a cationic fluorosurfactant is believed to provide for the deposition of a 'protective' layer on the surface being cleaned. This layer prevents or reduces the adhesion of soil subsequently applied to the surface.
• the layer also causes the surface cleaned to exhibit a lower surface energy and compositions according to the invention typically reduce the surface energy to less than 25 mN/meter.
• Suitable fluorosurfactant compounds can be broadly described as compounds which contain at least one CF 3 moiety and a group carrying a positive charge. We have determined that fluorosurfactants which include the CF 3 group have a larger depressive effect on the surface energy than those which include only CF 2 groups.
• the positive charge is borne on a nitrogen atom, and preferably the said nitrogen atom is quaternary.
• the fluorosurfactants employed in the present invention are of the general formula: (I) CF 3 -L-N + R 1 R 2 R 3 wherein L is a linking group which is preferably selected from linear or branched aliphatic or fluoro-aliphatic chains which may contain heteroatoms and R 1 , R 2 . and R 3 are preferably short chain alkyl groups, typically C1-C5 alkyl groups of which methyl groups are preferred: in an alternative, one of R 1 , R 2 or R 3 is itself a moiety of the form CF 3 -L-.
• the linking group L typically comprises a backbone which is at least six carbon or heteroatom units long. This provides sufficient spacing between the quaternary nitrogen and the -CF 3 group to ensure that the molecule exhibits appropriate surfactant behaviour.
• L is selected from the group comprising: (II) - (CF 2 ) n - (CH 2 ) m SCH 2 CHOH-CH 2 - where n + m is 6-22, (III) - R 4 CH 2 CH 2 CH(R 4 .CF 3 ) NHCOCH 2 - where R 4 is - (CF 2 ) n (CH2) m O(CO)- and n+m is 6 to 22, (IV) - (CF 2 ) n -(CH 2 ) m O(CO)CH 2 -CH 2 - where n + m is 6-22, (V) -R 5 CH 2 CH(R 5 .CF 3 )CH 2 - where R 5 is -(CF 2 ) n (CH2) m O(CO)- and n+m is 6 to 22, (VI) -(CF 2 ) n -(CH 2 ) m - where n + m is 6-22, (VII) -(CF 2 )
• fluorosurfactant materials are selected from the groups comprising: (IIa) F 3 -(CF 2 ) n -(CH 2 ) m SCH 2 CHOH-CH 2 -N + R 1 R 2 R 3 where n is 5-9 and m is 2, and R 1 R 2 and R 3 are -CH 3 .
• a suitable material being available as ZONYL FSD (TM) ex. Dupont.
• Suitable materials being found in the SURFLON (TM) range of surfactants available from Asahi Glass of Japan.
• VIIa F 3 -(CF 2 ) n -(CH 2 ) m SO 2 NH(CH 2 ) 3 -N + R 1 R 2 R 3 where n is 5-9 and m is 0, and R 1 R 2 and R 3 are -CH 3 .
• Suitable materials are available as FLUORAD FC135 (TM) ex. Minnesota Mining and Manufacturing.
• Preferred levels of cationic fluorosurfactant are the range 0.05-5%wt on product. Particularly preferred levels are in the range 0.1-2%wt on product, with levels of around 0.2%wt being most preferred as a compromise between cost and efficacy.
• Nonionic Surfactants :
• compositions of the present invention comprise a non-fluorinated nonionic surfactant.
• nonionic surfactant is believed to contribute significantly to the cleaning effectiveness of the compositions of the invention.
• Suitable nonionic detergent active compounds can be broadly described as compounds produced by the condensation of alkylene oxide groups, which are hydrophilic in nature, with an organic hydrophobic compound which may be aliphatic or alkyl aromatic in nature.
• the length of the hydrophilic or polyoxyalkylene radical which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.
• Particular examples include the condensation product of aliphatic alcohols having from 6 to 22 carbon atoms in either straight or branched chain configuration with ethylene oxide, such as a coconut oil ethylene oxide condensate having from 2 to 15 moles of ethylene oxide per mole of coconut alcohol; condensates of alkylphenols whose alkyl group contains from 6 to 12 carbon atoms with 5 to 25 moles of ethylene oxide per mole of alkylphenol; condensates of the reaction product of ethylenediamine and propylene oxide with ethylene oxide, the condensates containing from 40 to 80% of polyoxyethylene radicals by weight and having a molecular weight of from 5,000 to 11,000; tertiary amine oxides of structure R 3 N0, where one group R is an alkyl group of 8 to 18 carbon atoms and the others are each methyl, ethyl or hydroxy-ethyl groups, for instance dimethyldodecylamine oxide; tertiary phosphine oxides of
• nonionic surfactants are the ethoxylated alcohols having 6-14 carbons and 2-9 moles of ethoxylation.
• Suitable materials include IMBENTIN 91/35 OFA (TM), a C 9-11 nonionic having on average five moles of ethoxylation and NONIDET 91-6T (TM) a topped C 9-11 nonionic with an average of six moles of ethoxylation.
• nonionic surfactants are known to the skilled worker, as set forth in M.J.Schick 'Nonionic Surfactants', Marcel Dekker (1967) and subsequent editions of the same work.
• the amount of nonionic detergent active to be employed in the composition of the invention will generally be from 1 to 30%wt, preferably from 2 to 20%wt, and most preferably from 5 to 10%wt.
• Anionic surfactant may be present in the composition, but is preferably present at levels of less than 1% and is more preferably absent. It is believed that the presence of anionic detergents will cause the formation of a complex between the cationic and anionic detergents which will reduce the effectiveness of the compositions.
• the ratio of nonionic surfactant to the total of anionic and cationic surfactant is such that > 75% of the total surfactant present in the composition is nonionic.
• the overall surfactant content of compositions according to the present invention will generally be 1 to 30%.
• compositions of the present invention can contain other ingredients which aid in their cleaning performance and/or improve the physical properties of the composition. These components are not essential to the functioning of the invention.
• compositions of the invention comprise at least 0.5%wt of an organic amine, with a pK a of at least 8.0.
• This component is believed to function as ester-cleavage agent which assists cleaning of recalcitrant soils such as the pyrolised soils which are produced when fatty and/or proteinaceous foodstuffs are heated at the surface.
• organic amines with a lower pK a such as aniline are used they are ineffective in assisting cleaning.
• composition comprises 1-10% of an alkanolamine, with levels of 2-6%wt being particularly preferred.
• alkanolamines include: 2-amino-2-methyl-1-propanol, mono-ethanolamine and diethanolamine.
• 2-amino-2-methyl-1-propanol is the most preferred organic amine.
• Hydrophobic oils are optional components of compositions according to the present invention. Suitable oils include oils which rapidly dissolve triglyceride. When oils are present preferred oils include limonene, para-cymene, di-butyl ether and butyl butyrate.
• a further optional ingredient for compositions according to the invention is a suds regulating material, which can be employed in those compositions according to the invention which have a tendency to produce excessive suds in use.
• suds regulating materials are organic solvents, hydrophobic silica and silicone oils or hydrocarbons.
• Solvents are optional components of compositions according to the present invention. Where solvents are present, preferred solvents are of the form R 1 -0-(E0) m -(PO) n -R 2 , wherein R 1 and R 2 are independently C2-6 alkyl or H, but not both hydrogen, m and n are independently 0-5. More preferably, the solvent is selected from the group comprising di-ethylene glycol mono n-butyl ether, mono-ethylene glycol mono n-butyl ether, propylene glycol n-butyl ether, isopropanol, ethanol, butanol and mixtures thereof.
• Alternative solvents include the pyrrolid(in)ones, for example N-methyl pyrrolidinone.
• compositions according to the invention can also contain, in addition to the ingredients already mentioned, various other optional ingredients such as pH regulants, colourants, optical brighteners, soil suspending agents, enzymes, compatible bleaching agents, gel-control agents, freeze-thaw stabilisers, bactericides, preservatives, detergent hydrotropes, abrasives, perfumes and opacifiers.
• various other optional ingredients such as pH regulants, colourants, optical brighteners, soil suspending agents, enzymes, compatible bleaching agents, gel-control agents, freeze-thaw stabilisers, bactericides, preservatives, detergent hydrotropes, abrasives, perfumes and opacifiers.
• compositions according to the invention are packaged in a container adapted to produce a spray of 0.1-1.5ml of product per spraying operation, said spray having an average drop size in the range 30-300 microns.
• Suitable polymers include polyvinyl pyrrolidone, available in the marketplace as Polymer PVP K-90.
• Suitable levels of PVP polymer range upwards from 50ppm. Levels of 300-2000ppm are particularly preferred.
• compositions according to the invention comprise:
• Particularly preferred alkaline cleaning compositions according to the invention comprise:
• Particularly preferred neutral cleaning compositions according to the invention comprise:
• Aqueous compositions comprising nonionic surfactant, and a relatively low level of cationic surfactant were prepared as in Tables 1 below: using the following materials (all compositions in Table 1 are given in terms of wt% unless otherwise stated) :
• compositions were prepared at room temperature by mixing except where HEQ was used, this latter material being dissolved in three parts propylene glycol at 70 celcius and added to water, also at 70 celcius, while stirring.
• Results were obtained in four series over a period of time as it is commonly found that results should be only compared with those obtained by the same operator on the same day. These series of results are indicated as Series #1-4 in Table 1.
• the first five columns of table 1, give the identity of the fluoro and nonionic surfactants and their levels in the numbered examples. Examples whose number is followed by a star (*) are comparatives.
• compositions A-C are given below.
• vitreous enamel tiles (380x300mm) were cleaned using a fresh damp J-CLOTH (TM) using, in sequence, JIF cream (TM), then a commercially available brand of hand dishwashing liquid and finally calcite powder. After drying residual calcite was removed by buffing with a paper towel.
• TM fresh damp J-CLOTH
• TM JIF cream
• TM commercially available brand of hand dishwashing liquid
• calcite powder After drying residual calcite was removed by buffing with a paper towel.
• the surface energy gamma s /mN.m -1 was measured by the method of Grifalco, Good, Fowkes and Young (see Physical chemistry of Surfaces, A. A. Adamson, Wiley, New York [1990])), using the contact angle of hexadecane in Series #2 and Series #4 and dodecane in Series #1. Contact angles are given as 'Con' (in degrees) in Table 1 and calculated surface energies as 'CSE' (in mN/meter) in Table 1. For most household surfaces the surface energy after cleaning with conventional products is >25 mN/m. From the results in Series #1 of the examples it can be seen that significantly lower cleaning effort is required for compositions according to the invention than those which either contain no fluorosurfactant or only a very low and ineffective level of fluorosurfactant.
• Series #4 illustrates the effect of varying the level of one particular fluorosurfactant. It can be seen that for this particular material, little or no benefit is obtained at inclusion levels of below 0.05%wt but that an increasing benefit as compared with the control is found as the level of fluorosurfactant is increased.

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• Chemical & Material Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Wood Science & Technology (AREA)
• Organic Chemistry (AREA)
• Detergent Compositions (AREA)

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• 1997
  • 1997-03-19 GB GBGB9705682.4A patent/GB9705682D0/en active Pending
• 1998
  • 1998-03-05 EP EP98301652A patent/EP0866115A3/fr not_active Withdrawn
  • 1998-03-09 CA CA 2231598 patent/CA2231598A1/fr not_active Abandoned
  • 1998-03-17 JP JP6636398A patent/JPH10279990A/ja active Pending

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